US10135077B2 - Corrosion resistant metal bipolar plate for a PEMFC including a radical scavenger - Google Patents

Corrosion resistant metal bipolar plate for a PEMFC including a radical scavenger Download PDF

Info

Publication number
US10135077B2
US10135077B2 US14/620,530 US201514620530A US10135077B2 US 10135077 B2 US10135077 B2 US 10135077B2 US 201514620530 A US201514620530 A US 201514620530A US 10135077 B2 US10135077 B2 US 10135077B2
Authority
US
United States
Prior art keywords
middle layer
radical scavenging
scavenging material
layer
cerium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US14/620,530
Other languages
English (en)
Other versions
US20160240865A1 (en
Inventor
Shinichi Hirano
Mark Stephen RICKETTS
Kerrie K. GATH
Jun Yang
Chunchuan Xu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ford Global Technologies LLC
Original Assignee
Ford Global Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ford Global Technologies LLC filed Critical Ford Global Technologies LLC
Priority to US14/620,530 priority Critical patent/US10135077B2/en
Assigned to FORD GLOBAL TECHNOLOGIES, LLC reassignment FORD GLOBAL TECHNOLOGIES, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: Gath, Kerrie K., HIRANO, SHINICHI, RICKETTS, MARK STEPHEN, XU, CHUNCHUAN, YANG, JUN
Priority to CN201610076453.1A priority patent/CN105895927B/zh
Priority to DE102016102393.0A priority patent/DE102016102393A1/de
Publication of US20160240865A1 publication Critical patent/US20160240865A1/en
Application granted granted Critical
Publication of US10135077B2 publication Critical patent/US10135077B2/en
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H01M8/0208—Alloys
    • H01M8/021—Alloys based on iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0215—Glass; Ceramic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8694—Bipolar electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
    • H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y02T90/32—
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells

Definitions

  • the present disclosure relates to corrosion resistant metal bipolar plates including a radical scavenger.
  • Fuel cells for example, hydrogen fuel cells, are one possible alternative energy source for powering vehicles.
  • fuel cells include a negative electrode (anode), an electrolyte, and a positive electrode (cathode).
  • the electrolyte is a solid, proton-conducting membrane that is electrically insulating but allows protons to pass through.
  • the fuel source such as hydrogen
  • the fuel source is introduced at the anode using a bipolar or flow field plate where it reacts with a catalyst and splits into electrons and protons.
  • the protons travel through the electrolyte to the cathode and the electrons pass through an external circuit and then to the cathode.
  • oxygen in air introduced from another bipolar plate reacts with the electrons and the protons at another catalyst to form water.
  • One or both of the catalysts are generally formed of a noble metal or a noble metal alloy, typically platinum or a platinum alloy.
  • the bipolar plates in the PEMFC have two primary functions. First, the bipolar plates feed reactant gases (e.g., hydrogen and air) to the membrane electrode assembly (MEA). Second, the bipolar plates collect current from the MEA. In order to collect current, the bipolar plates must be conductive or have a conductive coating. Typically, the bipolar plates are formed from a conductive carbon-based material, such as a carbon composite, which may be fabricated by a molding process.
  • reactant gases e.g., hydrogen and air
  • MEA membrane electrode assembly
  • the bipolar plates collect current from the MEA. In order to collect current, the bipolar plates must be conductive or have a conductive coating.
  • the bipolar plates are formed from a conductive carbon-based material, such as a carbon composite, which may be fabricated by a molding process.
  • a fuel cell bipolar plate may include a steel substrate, a middle layer contacting the steel substrate and including a bulk material and a radical scavenging material comprising cerium, and a conductive layer contacting the middle layer.
  • the cerium includes metallic cerium or a cerium oxide.
  • the middle layer bulk material may include a carbide or a nitride of chromium or titanium.
  • the conductive layer may comprise a conductive carbon, for example, diamond-like carbon (DLC), graphite, graphene, and/or carbon particles.
  • the radical scavenging material comprises 0.01 to 30 wt % of the middle layer. In another embodiment, the radical scavenging material comprises 0.1 to 15 wt % of the middle layer.
  • the middle layer may have a thickness of 5 nm to 10 ⁇ m.
  • a fuel cell bipolar plate may include a steel substrate, a middle layer contacting the steel substrate and including a bulk material and a radical scavenging material that scavenges at least one of hydroxyl radicals and perhydroxyl radicals, and a conductive layer including a conductive carbon contacting the middle layer.
  • the radical scavenging material includes cerium, for example, metallic cerium or a cerium oxide.
  • the middle layer bulk material may include a carbide or a nitride of chromium or titanium.
  • the conductive carbon includes one or more of a diamond-like carbon (DLC), graphite, graphene, and carbon particles.
  • the radical scavenging material may comprise 0.1 to 15 wt % of the middle layer.
  • a method of forming a radical scavenging coating on a fuel cell bipolar plate may include applying a middle layer to a steel substrate, the middle layer including a bulk material and a radical scavenging material including cerium, and applying a conductive layer to the middle layer.
  • the cerium is deposited as metallic cerium or cerium oxide.
  • the bulk material may include a carbide or a nitride of chromium or titanium.
  • the conductive layer may comprise a conductive carbon.
  • applying the middle layer to the steel substrate includes applying the bulk material and the radical scavenging material such that the radical scavenging material comprises 0.01 to 30 wt % of the middle layer. Applying the middle layer to the steel substrate may include co-sputtering the bulk material and the radical scavenging material.
  • FIG. 1 is an exploded view of the components of a fuel cell
  • FIG. 2 is a schematic cross-section of a fuel cell
  • FIG. 3 is a schematic cross-section of a bipolar plate having a coating including a radical scavenger, according to an embodiment.
  • the PEMFC 10 generally includes a negative electrode (anode) 12 and a positive electrode (cathode) 14 , separated by a proton exchange membrane (PEM) 16 (also a polymer electrolyte membrane).
  • the anode 12 and the cathode 14 may each include a gas diffusion layer (GDL) 18 , a catalyst layer 20 , and a bipolar or flow field plate 22 which forms a gas channel 24 .
  • the catalyst layer 20 may be the same for the anode 12 and the cathode 14 , however, the anode 12 may have a catalyst layer 20 ′ and the cathode 14 may have a different catalyst layer 20 ′′.
  • the catalyst layer 20 ′ may facilitate the splitting of hydrogen atoms into hydrogen ions and electrons while the catalyst layer 20 ′′ facilitates the reaction of oxygen gas and electrons to form water.
  • the anode 12 and cathode 14 may each include a microporous layer (MPL) 26 disposed between the GDL 18 and the catalyst layer 20 .
  • MPL microporous layer
  • the PEM 16 may be any suitable PEM known in the art, such as a fluoropolymer, for example, Nafion (a sulfonated tetrafluoroethylene based fluoropolymer-copolymer).
  • the GDL 18 may be formed of materials and by methods known in the art.
  • the GDL 18 may be formed from carbon fiber based paper and/or cloth.
  • GDL materials are generally highly porous (having porosities of about 80%) to allow reactant gas transport to the catalyst layer (which generally has a thickness of about 10-15 ⁇ m), as well as liquid water transport from the catalyst layer.
  • GDLs may be treated to be hydrophobic with a non-wetting polymer such as polytetrafluoroethylene (PTFE, commonly known by the trade name Teflon).
  • An MPL may be coated to the GDL side facing the catalyst layer to assist mass transport.
  • the MPL may be formed of materials and by methods known in the art, for example, carbon powder and a binder (e.g., PTFE particles).
  • the catalyst layer 20 may include a noble metal or a noble metal alloy, such as platinum or a platinum alloy.
  • the catalyst layer may include a catalyst support, which may support or have deposited thereon a catalyst material layer.
  • the bipolar plates 22 may have channels 24 defined therein for carrying gases.
  • the channels 24 may carry air or fuel (e.g., hydrogen).
  • the plates 22 and channels 24 may be rotated 90 degrees relative to each other.
  • the plates 22 and channels may be oriented in the same direction.
  • Bipolar plate materials need to be electrically conductive and corrosion resistant under proton exchange membrane fuel cell (PEMFC) operating conditions to ensure that the bipolar plate perform its functions—feeding reactant gases to the membrane electrode assembly (MEA) and collecting current from the MEA.
  • PEMFC proton exchange membrane fuel cell
  • metal bipolar plates may offer several advantages over carbon-based plates.
  • the use of metal may enable bipolar plates to be thinner, which may reduce the size of the fuel cell stack.
  • it may enable the manufacturer to take advantage of high volume manufacturing processes, such as stamping, corrugated rolling, or others, which may reduce the cost of the fuel cell stack.
  • Metal bipolar plates may have disadvantages, as well, however.
  • One issue that affects metal bipolar plates is the leaching or elution of elements from the metal into the fuel cell during operation.
  • a metal that has been proposed for use in bipolar plates is stainless steel.
  • Stainless steel is a low-cost, high strength, and readily available material.
  • bare stainless steel alloys may form insulating passive layers under fuel cell operating conditions, resulting in higher surface electrical resistance. Therefore, to make stainless steel a practical substrate for bipolar plates, either corrosion resistant and electrically conductive coatings or particles must be applied to the stainless steel plate.
  • a main obstacle to the use of stainless steel as the bi-polar plate is that the constituents of stainless steel substrate may slowly elute out through coating defects during fuel cell operation.
  • One of the most common coating defects is pinholes, or small point-defects having a size of about several angstroms to tens of nanometers.
  • the eluted metal ions may poison or contaminate the fuel cell stack components (such as the MEA).
  • some transition metal ions such as ferric ions (Fe +2 and Fe +3 ) may react with hydrogen peroxide (a by-product of the oxygen reduction reaction (ORR)) in PEMFCs to form radicals, such as hydroxyl radicals (HO.) and/or perhydroxyl radicals (HOO.). Radicals may then chemically attack the membrane materials, which may affect the performance and/or longevity of the fuel cell.
  • Iron is the main elemental component of stainless steel, therefore, elution of iron may be problematic.
  • SS stainless steel
  • Au gold
  • pinholes will almost always exist during film processing, requiring that the layer be relatively thick (e.g., at least 10 nm). Gold is expensive, therefore, using thicker layers is not desirable.
  • gold is soft, so a 10 nm layer may be easily scratched during the assembly of the fuel cell, reducing or eliminating the effectiveness of the coating.
  • the gold layer may change its morphology during corrosion testing, forming spheres or globules.
  • Another approach is to coat the SS plate with a layer of conductive metal oxide anchored with gold or iridium (Ir) nano-dots.
  • the metal oxides are about 250 nm thick, which, when combined with the Au/Ir nano-dots, leads to reduced electrical conductivity.
  • the present disclosure describes a metal bipolar plate including a coating having a radical scavenger, as well as methods for forming the coating.
  • the disclosed coating may reduce or eliminate the number of radicals produced in the fuel cell due to elution.
  • the disclosed coating may therefore allow metallic bipolar plates to be used, which may increase volumetric power density of the fuel cell stack, and may do so without an increase in cost.
  • a metal bipolar plate 22 having a substrate 32 and a coating 34 .
  • the substrate may be metallic, such as steel, titanium, alloys thereof, or others.
  • the substrate 32 is formed of stainless steel, for example austenitic stainless steel (e.g., 301, 303, 304, 316 or 316L).
  • austenitic stainless steel e.g., 301, 303, 304, 316 or 316L.
  • a middle layer 36 and disposed over and contacting the middle layer 36 is a conductive layer 38 .
  • the middle layer 36 and the conductive layer 38 form the coating 34 , which may be electrically conductive and corrosion resistant.
  • the primary purposes of the middle layer 36 may be to improve adhesion between the conductive layer 38 and the substrate 32 and to reduce elution of ions from the substrate 32 into the fuel cell environment.
  • the conductive layer 38 may primarily be an electrical conductor such that the bipolar plate 22 can collect current from the MEA within the fuel cell.
  • the conductive layer 38 may also assist in preventing or reducing corrosion of or elution from the substrate 32 .
  • the middle layer 36 may include any suitable electrically conductive bulk material that provides good adhesion to both the substrate 32 and the conductive layer 38 .
  • the middle layer may include a carbide and/or nitride of chromium (Cr) and/or titanium (Ti).
  • Cr chromium
  • Ti titanium
  • the middle layer may include compositions that vary from the exact formulas above (e.g., 1:1 ratio of Cr and N).
  • the bulk material may include chromium and nitrogen in a Cr:N ratio of 0.7:1.3 to 1.3:0.7 (at %), or any sub-range therein.
  • the Cr:N ratio may be 0.8:1.2 to 1.2:0.8 or 0.9:1.1 to 1.1:0.9.
  • the same ratios and ratio ranges may also apply to titanium and nitrogen (e.g., Ti:N) or titanium and carbon (e.g., Ti:C).
  • the bulk material may include chromium and nitrogen in a Cr:N ratio of 2.5:2.5 to 3.5:1.5 (at %), or any sub-range therein.
  • the Cr:N ratio may be 2.7:2.3 to 3.3:1.7 or 2.9:2.1 to 3.1:1.9.
  • the middle layer may have any suitable thickness to provide good adhesion and/or good elution reduction.
  • the middle layer may have a thickness of 5 nm to 10 ⁇ m, or any sub-range therein.
  • the middle layer may have a thickness from 10 nm to 10 ⁇ m, 0.1 to 5 ⁇ m, 0.1 to 2 ⁇ m, 0.01 to 1 ⁇ m, 0.01 to 0.5 ⁇ m, 0.01 to 0.3 ⁇ m, or about 0.2 ⁇ m.
  • the conductive layer 38 may include any suitable electrically conductive material that is non-reactive with the components of the fuel cell.
  • the conductive layer 38 may include a form of conductive carbon, such as diamond-like carbon (DLC), graphite, graphene, carbon particles (e.g., carbon black), or others.
  • Other suitable materials for the conductive layer may include noble metals, such as gold, iridium, ruthenium, tantalum, alloys or oxides thereof, or others.
  • the conductive layer 38 may have any suitable thickness for providing sufficient conductivity to the coating 34 . In one embodiment, the conductive layer 38 may have a thickness of a micron or less.
  • the conductive layer 38 may have a thickness of 1 to 500 nm, or any sub-range therein, such as 1 to 250 nm, 1 to 100 nm, 1 to 50 nm, 1 to 25 nm, 1 to 15 nm, 1 to 10 nm, 5 to 10 nm, or 1 to 5 nm.
  • eluted ions such as ferric ions
  • peroxide may react with peroxide to form free radicals (referred to herein simply as “radicals”).
  • the formed radicals may thereafter chemically react with the membrane materials in the fuel cell, which may reduce performance and the longevity or lifetime of the fuel cell.
  • a radical scavenging material or radical scavenger 40 may be included within the coating 34 .
  • the radical scavenger 40 may be included in the middle layer 36 and/or the conductive layer 38 .
  • the radical scavenger material may be included as an alloying element or composition, as a dopant or doping agent, or as an additional layer.
  • the radical scavenging material may be a material that scavenges hydroxyl radicals (HO.) and/or perhydroxyl radicals (HOO.).
  • the radical scavenging material 40 is cerium and/or a cerium oxide, CeO x .
  • the cerium may be metallic or pure cerium in any oxidation state (e.g., 0 to +4).
  • the cerium oxide may be cerium(IV) oxide, CeO 2 , or other forms of cerium oxide (e.g., cerium(III) oxide, Ce 2 O 3 ).
  • Cerium oxide is sometimes used as an electrolyte in solid oxide fuel cells (SOFCs), however, in the present disclosure they may be incorporated into the bipolar plate coating 34 to reduce radicals.
  • Cerium oxide may decompose peroxide and scavenge radicals, for example, through the mechanism shown in reactions (3) to (7) below: Ce +4 H 2 O 2 ⁇ Ce +3 +HOO ⁇ +H + (3) Ce +4 +HOO. ⁇ Ce +3 +O 2 +H + (4) Ce +3 +HOO.+H + ⁇ Ce +3 H 2 O 2 (5) CeOx+HO. ⁇ CeO x ⁇ 1 +O 2 +H + (6) Ce +3 +HO.+H + ⁇ H 2 O+Ce +4 (7)
  • the scavenging material 40 (e.g., cerium) may not be consumed during the radical scavenging reactions. Therefore, the radical scavenging material 40 may continue to scavenge radicals without being depleted, thereby increasing the lifetime of the material 40 and the fuel cell.
  • the radical scavenging material is an oxide of a rare earth metal or transition metals.
  • a “transition metal” may be a metal in groups 3-12 of the periodic table. In one embodiment, the metal may possess adjacent oxidation states, for example, M 3+ and M 4+ .
  • Non-limiting examples of rare earth metals which may be used include terbium, europium and cerium.
  • Non-limiting examples of transition metals which may be used include manganese, chromium, ruthenium, and vanadium.
  • the middle layer 36 may be applied or deposited using any suitable method known in the art, such as chemical or physical vapor deposition (CVD or PVD).
  • CVD processes that may be suitable include atmospheric, vacuum, aerosol assisted, plasma assisted, atomic layer CVD, wet chemical, CCVD, or others.
  • PVD processes that may be suitable include cathodic arc deposition, electron beam physical vapor deposition, evaporative deposition, pulsed laser deposition, sputter deposition (e.g., DC or RF magnetron sputtering), or others.
  • the radical scavenging material 40 may be incorporated into the middle layer 36 using any suitable method, depending on the deposition technique used to form the middle layer 36 .
  • the radical scavenging material 40 e.g., cerium oxide
  • the middle layer 36 may be deposited by sputtering (e.g., magnetron sputtering) and the radical scavenging material 40 (e.g., cerium or cerium oxide) may be co-sputtered onto the substrate 32 along with the middle layer material.
  • the scavenging material may also be deposited in a reactive atmosphere (e.g., oxygen) to form an oxide (e.g., cerium oxide).
  • the scavenging material may be deposited in any suitable oxidative state.
  • cerium may be deposited in any state from 0 to +4.
  • the radical scavenging material 40 may be added using other doping techniques known in the art.
  • the radical scavenging material 40 e.g., cerium or cerium oxide
  • the radical scavenging material 40 may be diffused into the middle layer 36 from a gas, liquid, or solid.
  • separate layers of the middle layer material and the radical scavenging material may be deposited and then heat treated to diffuse into one another.
  • the radical scavenging material 40 may also be added using ion implantation.
  • Other methods, such as CVD epitaxy and other techniques used in, for example, semiconductor doping processes may also be used.
  • the radical scavenging material 40 may be present in the middle layer 36 in a quantity sufficient to scavenge all or substantially all of the iron ions that are present or produced. However, the scavenging material 40 may also be present at a quantity that does not substantially interfere with the properties of the middle layer 36 , such as conductivity and adhesion. In at least one embodiment, the radical scavenging material comprises from 0.01 to 30 wt % of the middle layer 36 , or any sub-range therein.
  • the radical scavenging material may comprise from 0.01 to 20 wt %, 0.1 to 20 wt %, 0.1 to 15 wt %, 1 to 15 wt %, 5 to 15 wt %, 8 to 12 wt %, 1 to 10 wt %, 0.01 to 10 wt %, 0.1 to 10 wt %, 0.1 to 5 wt %, or about 5 wt %, about 10 wt %, or about 15 wt % of the middle layer 36 .
  • a metal bipolar plate including a coating
  • the coating may include a middle or intermediate layer covering and contacting the metal substrate and a conductive layer covering and contacting the middle layer.
  • the middle layer may include a radical scavenging material, such as cerium or a cerium oxide, which may react with the radicals and other materials or chemical components within the fuel cell to neutralize the radicals before they attack the components of the fuel cell, such as the membranes.
  • the radical scavenging material may not be consumed during the reaction, thereby allowing the reaction to be recursive and continue neutralizing radicals that may continue to form.
  • the inclusion of the radical scavenging material in the coating may allow the use of steel (e.g., stainless steel) as the substrate for a bipolar plate in a fuel cell (e.g., PEMFC).
  • steel e.g., stainless steel
  • Stainless steel is relatively cheap and easy to form and shape. It is also strong and can provide sufficient mechanical and electrical properties in very thin form factors.
  • steel has previously been disfavored for bipolar plates due to the elution of iron ions that produce radicals within the fuel cell. Accordingly, by allowing the bipolar plate to be made of stainless steel, the disclosed coating may facilitate the formation of smaller, cheaper, and more robust fuel cells.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Composite Materials (AREA)
  • Ceramic Engineering (AREA)
  • Fuel Cell (AREA)
US14/620,530 2015-02-12 2015-02-12 Corrosion resistant metal bipolar plate for a PEMFC including a radical scavenger Active 2035-04-18 US10135077B2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US14/620,530 US10135077B2 (en) 2015-02-12 2015-02-12 Corrosion resistant metal bipolar plate for a PEMFC including a radical scavenger
CN201610076453.1A CN105895927B (zh) 2015-02-12 2016-02-03 用于pemfc的包括自由基捕获剂的耐腐蚀金属双极板
DE102016102393.0A DE102016102393A1 (de) 2015-02-12 2016-02-11 Korrosionsbeständige bipolarplatte aus metall für eine protonenaustauschmembran-brennstoffzelle (pemfc) mit radikalfänger

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US14/620,530 US10135077B2 (en) 2015-02-12 2015-02-12 Corrosion resistant metal bipolar plate for a PEMFC including a radical scavenger

Publications (2)

Publication Number Publication Date
US20160240865A1 US20160240865A1 (en) 2016-08-18
US10135077B2 true US10135077B2 (en) 2018-11-20

Family

ID=56551729

Family Applications (1)

Application Number Title Priority Date Filing Date
US14/620,530 Active 2035-04-18 US10135077B2 (en) 2015-02-12 2015-02-12 Corrosion resistant metal bipolar plate for a PEMFC including a radical scavenger

Country Status (3)

Country Link
US (1) US10135077B2 (de)
CN (1) CN105895927B (de)
DE (1) DE102016102393A1 (de)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106654315B (zh) * 2016-12-15 2019-03-05 大连理工大学 一种石墨烯增强表面的燃料电池用高性能双极板及其制备方法
DE102017202679A1 (de) * 2017-02-20 2018-08-23 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Bipolarplatte für elektrochemische Zellen sowie ein Herstellungsverfahren
CN107302094B (zh) * 2017-06-15 2019-10-11 常州翊迈新材料科技有限公司 燃料电池金属双极板超导电超耐蚀的功能涂层及制备方法
KR101860870B1 (ko) * 2017-07-14 2018-05-29 (주)상아프론테크 Pemfc용 라디칼 스캐빈져 조성물, pemfc용 라디칼 스캐빈져 및 이의 제조방법
CN107761060B (zh) * 2017-09-27 2020-05-19 南京工业大学 电池用金属极板表面耐蚀导电复合涂层、电池用金属极板及其制备方法
KR102339036B1 (ko) * 2017-09-29 2021-12-13 코오롱인더스트리 주식회사 라디칼 분해 촉매, 이의 제조 방법, 이를 포함하는 막-전극 어셈블리, 그리고 이를 포함하는 연료 전지
EP3604606A1 (de) 2018-08-02 2020-02-05 Centre de Recherches Métallurgiques ASBL - Centrum voor Research in de Metallurgie VZW Beschichtung zur verringerung des kontaktwiderstands eines passiven metallsubstrats vor der aufbringung einer leiterschicht, die eine korrosionsfestigkeit bewirkt
CN109560289B (zh) * 2018-12-26 2023-11-28 浙江锋源氢能科技有限公司 一种金属双极板及其制备方法以及燃料电池
CN113795959A (zh) * 2019-05-08 2021-12-14 可隆工业株式会社 自由基清除剂、其制备方法和包含其的膜-电极组件
CN110129727B (zh) * 2019-05-22 2021-08-03 上海佑戈金属科技有限公司 用于燃料电池金属双极板的预涂镀金属卷带的制备方法
CN110449574B (zh) * 2019-08-05 2021-11-09 上海世系新材料有限公司 一种低缺陷石墨烯包覆铝粉微粒的制备方法
EP3778982B1 (de) * 2019-08-14 2023-07-05 IHI Hauzer Techno Coating B.V. Verfahren zum beschichten einer oder mehrerer metallkomponenten eines brennstoffzellenstapels, komponente eines brennstoffzellenstapels und vorrichtung zum beschichten einer oder mehrerer komponenten eines brennstoffzellenstapels
DE102020202375A1 (de) 2020-02-25 2021-08-26 Robert Bosch Gesellschaft mit beschränkter Haftung Brennstoffzellenstapel und Verfahren zum Herstellen desselben
CN111933965A (zh) * 2020-07-24 2020-11-13 苏州敦胜新能源科技有限公司 一种高温燃料电池双极板抗氧化镀层
FR3126428A1 (fr) * 2021-08-31 2023-03-03 Hydromecanique Et Frottement Procédé de dépôt de carbone sur un substrat
CN117254081B (zh) * 2023-09-19 2024-05-14 上海大学 一种抗老化质子交换膜及其制备方法与膜电极组件

Citations (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030190515A1 (en) * 2002-04-03 2003-10-09 Brady Michael P. Corrosion resistant metallic bipolar plate
US20040186201A1 (en) * 2003-03-07 2004-09-23 James Stoffer Corrosion resistant coatings containing carbon
US20060019142A1 (en) * 2004-07-20 2006-01-26 Abd Elhamid Mahmoud H Enhanced stability bipolar plate
US20060032525A1 (en) * 2004-08-13 2006-02-16 Olsen Larry C Boron carbide films with improved thermoelectric and electric properties
US20060194095A1 (en) * 2005-02-28 2006-08-31 Gayatri Vyas Method to make conductive hydrophilic fuel cell elements
US20070243452A1 (en) * 2006-04-14 2007-10-18 Applied Materials, Inc. Reliable fuel cell electrode design
US20070287057A1 (en) 2006-06-09 2007-12-13 Elhamid Mahmoud H Abd Method for making a hydrophilic corrosion resistant coating on low grade stainless steel/alloys for bipolar plates
CN101092688A (zh) 2007-05-28 2007-12-26 大连理工大学 质子交换膜燃料电池不锈钢双极板离子镀膜改性方法
US20080038625A1 (en) 2006-08-10 2008-02-14 Gm Global Technology Operations, Inc. Fast Recycling Process For Ruthenium, Gold and Titanium Coatings From Hydrophilic PEM Fuel Cell Bipolar Plates
US20080076004A1 (en) 2006-07-26 2008-03-27 Gm Global Technology Operations, Inc. Method For Making Super-Hydrophilic And Electrically Conducting Surfaces For Fuel Cell Bipolar Plates
US20080096078A1 (en) * 2004-12-24 2008-04-24 Asahi Kasei Kabushiki Kaisha Highly Durable Electrode Catalyst Layer
US20080199767A1 (en) 2007-02-20 2008-08-21 Commonwealth Scientific And Industrial Research Organisation Corrosion-resistant interconnects for fuel cells
US20090130502A1 (en) * 2006-02-17 2009-05-21 Monsanto Technology Llc Transition metal-containing catalysts and processes for their preparation and use as fuel cell catalysts
US7553517B1 (en) * 2005-09-15 2009-06-30 The United States Of America As Represented By The United States Department Of Energy Method of applying a cerium diffusion coating to a metallic alloy
US20090317686A1 (en) * 2008-06-20 2009-12-24 Gm Global Technology Operations, Inc. Fuel cell with an electrolyte stabilizing agent and process of making the same
US20100035123A1 (en) * 2004-02-17 2010-02-11 Narayanan Sekharipuram R Low Pt content direct methanol fuel cell anode catalyst: nanophase PtRuNiZr
US20100330389A1 (en) 2009-06-25 2010-12-30 Ford Motor Company Skin pass for cladding thin metal sheets
US20110033784A1 (en) 2008-02-27 2011-02-10 Impact Coatings Ab Electrode with a coating, method in production thereof and use of a material
US20110165501A1 (en) 2008-07-16 2011-07-07 Kuroudo Maeda Fuel cell separator and fuel cell
US20110229791A1 (en) * 2008-11-28 2011-09-22 Nissan Motor Co., Ltd. Sealing structure and fuel cell having the sealing structure
US20110287336A1 (en) 2008-11-25 2011-11-24 Nissan Motor Co., Ltd. Electrical conductive member and polymer electrolyte fuel cell using the same
US8101319B2 (en) 2004-05-20 2012-01-24 GM Global Technology Operations LLC Approach to make a high performance membrane electrode assembly (MEA) for a PEM fuel cell
US8182963B2 (en) 2009-07-10 2012-05-22 GM Global Technology Operations LLC Low-cost manganese-stabilized austenitic stainless steel alloys, bipolar plates comprising the alloys, and fuel cell systems comprising the bipolar plates
US20120141919A1 (en) * 2010-12-02 2012-06-07 Hyundai Motor Company Fuel cell electrode and method for manufacturing membrane-electrode assembly using the same
US8232026B2 (en) 2010-10-14 2012-07-31 Ford Global Technologies, Llc Bipolar plates for electrochemical cells
US20120231374A1 (en) * 2009-12-25 2012-09-13 Toyota Jidosha Kabushiki Kaisha Bipolar plate for fuel cell and method for producing the same
US8268466B2 (en) 2001-11-02 2012-09-18 Greatbatch Ltd. Method for coating noble metals on titanium current collectors for use in nonaqueous Li/CFx cells
US20130183602A1 (en) * 2012-01-17 2013-07-18 Basf Se Proton-conducting membrane and use thereof
WO2013124690A1 (en) 2012-02-24 2013-08-29 Teer Coatings Limited Coating with conductive and corrosion resistance characteristics
US20130230793A1 (en) 2012-02-23 2013-09-05 Treadstone Technologies, Inc. Corrosion resistant and electrically conductive surface of metal
US8592098B2 (en) 2010-03-22 2013-11-26 Hyundai Hysco Metal separator for fuel cell and method of manufacturing the same
US8623301B1 (en) * 2008-04-09 2014-01-07 C3 International, Llc Solid oxide fuel cells, electrolyzers, and sensors, and methods of making and using the same
US8778566B2 (en) 2009-08-21 2014-07-15 Hyundai Hysco Metal separator plate for fuel cell having coating film formed on surface and method for producing same
US8778562B2 (en) 2012-06-11 2014-07-15 GM Global Technology Operations LLC Method of depositing durable thin gold coating on fuel cell bipolar plates
US8859164B2 (en) 2011-02-15 2014-10-14 Ford Global Technologies, Llc Bipolar plates and electrochemical cells employing the same
US20160233523A1 (en) * 2013-09-24 2016-08-11 Toyota Jidosha Kabushiki Kaisha Fuel cell separator, fuel cell, and manufacturing method of fuel cell separator

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007032116A1 (de) * 2007-07-09 2009-01-15 Thyssenkrupp Steel Ag Bipolarplatte für eine Brennstoffzelle und Brennstoffzellen-Stack
US8999595B2 (en) * 2010-11-30 2015-04-07 GM Global Technology Operations LLC Fuel cells having improved durability
US9379403B2 (en) * 2011-08-26 2016-06-28 Asahi Glass Company, Limited Polymer electrolyte membrane and membrane/electrode assembly for polymer electrolyte fuel cell
US9685674B2 (en) * 2011-12-20 2017-06-20 Toray Industries, Inc. Polymer electrolyte composition, and polymer electrolyte membrane, membrane electrode assembly and solid polymer fuel cell each using same

Patent Citations (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8268466B2 (en) 2001-11-02 2012-09-18 Greatbatch Ltd. Method for coating noble metals on titanium current collectors for use in nonaqueous Li/CFx cells
US20030190515A1 (en) * 2002-04-03 2003-10-09 Brady Michael P. Corrosion resistant metallic bipolar plate
US20040186201A1 (en) * 2003-03-07 2004-09-23 James Stoffer Corrosion resistant coatings containing carbon
US20100035123A1 (en) * 2004-02-17 2010-02-11 Narayanan Sekharipuram R Low Pt content direct methanol fuel cell anode catalyst: nanophase PtRuNiZr
US8101319B2 (en) 2004-05-20 2012-01-24 GM Global Technology Operations LLC Approach to make a high performance membrane electrode assembly (MEA) for a PEM fuel cell
US20060019142A1 (en) * 2004-07-20 2006-01-26 Abd Elhamid Mahmoud H Enhanced stability bipolar plate
US20060032525A1 (en) * 2004-08-13 2006-02-16 Olsen Larry C Boron carbide films with improved thermoelectric and electric properties
US20080096078A1 (en) * 2004-12-24 2008-04-24 Asahi Kasei Kabushiki Kaisha Highly Durable Electrode Catalyst Layer
US20060194095A1 (en) * 2005-02-28 2006-08-31 Gayatri Vyas Method to make conductive hydrophilic fuel cell elements
US7553517B1 (en) * 2005-09-15 2009-06-30 The United States Of America As Represented By The United States Department Of Energy Method of applying a cerium diffusion coating to a metallic alloy
US20090130502A1 (en) * 2006-02-17 2009-05-21 Monsanto Technology Llc Transition metal-containing catalysts and processes for their preparation and use as fuel cell catalysts
US20070243452A1 (en) * 2006-04-14 2007-10-18 Applied Materials, Inc. Reliable fuel cell electrode design
US20070287057A1 (en) 2006-06-09 2007-12-13 Elhamid Mahmoud H Abd Method for making a hydrophilic corrosion resistant coating on low grade stainless steel/alloys for bipolar plates
US20080076004A1 (en) 2006-07-26 2008-03-27 Gm Global Technology Operations, Inc. Method For Making Super-Hydrophilic And Electrically Conducting Surfaces For Fuel Cell Bipolar Plates
US20080038625A1 (en) 2006-08-10 2008-02-14 Gm Global Technology Operations, Inc. Fast Recycling Process For Ruthenium, Gold and Titanium Coatings From Hydrophilic PEM Fuel Cell Bipolar Plates
US20080199767A1 (en) 2007-02-20 2008-08-21 Commonwealth Scientific And Industrial Research Organisation Corrosion-resistant interconnects for fuel cells
CN101092688A (zh) 2007-05-28 2007-12-26 大连理工大学 质子交换膜燃料电池不锈钢双极板离子镀膜改性方法
US20110033784A1 (en) 2008-02-27 2011-02-10 Impact Coatings Ab Electrode with a coating, method in production thereof and use of a material
US8623301B1 (en) * 2008-04-09 2014-01-07 C3 International, Llc Solid oxide fuel cells, electrolyzers, and sensors, and methods of making and using the same
US20090317686A1 (en) * 2008-06-20 2009-12-24 Gm Global Technology Operations, Inc. Fuel cell with an electrolyte stabilizing agent and process of making the same
US20110165501A1 (en) 2008-07-16 2011-07-07 Kuroudo Maeda Fuel cell separator and fuel cell
US20110287336A1 (en) 2008-11-25 2011-11-24 Nissan Motor Co., Ltd. Electrical conductive member and polymer electrolyte fuel cell using the same
US20110229791A1 (en) * 2008-11-28 2011-09-22 Nissan Motor Co., Ltd. Sealing structure and fuel cell having the sealing structure
US20100330389A1 (en) 2009-06-25 2010-12-30 Ford Motor Company Skin pass for cladding thin metal sheets
US8182963B2 (en) 2009-07-10 2012-05-22 GM Global Technology Operations LLC Low-cost manganese-stabilized austenitic stainless steel alloys, bipolar plates comprising the alloys, and fuel cell systems comprising the bipolar plates
US8778566B2 (en) 2009-08-21 2014-07-15 Hyundai Hysco Metal separator plate for fuel cell having coating film formed on surface and method for producing same
US20120231374A1 (en) * 2009-12-25 2012-09-13 Toyota Jidosha Kabushiki Kaisha Bipolar plate for fuel cell and method for producing the same
US8592098B2 (en) 2010-03-22 2013-11-26 Hyundai Hysco Metal separator for fuel cell and method of manufacturing the same
US8232026B2 (en) 2010-10-14 2012-07-31 Ford Global Technologies, Llc Bipolar plates for electrochemical cells
US20120141919A1 (en) * 2010-12-02 2012-06-07 Hyundai Motor Company Fuel cell electrode and method for manufacturing membrane-electrode assembly using the same
US8859164B2 (en) 2011-02-15 2014-10-14 Ford Global Technologies, Llc Bipolar plates and electrochemical cells employing the same
US20130183602A1 (en) * 2012-01-17 2013-07-18 Basf Se Proton-conducting membrane and use thereof
US20130230793A1 (en) 2012-02-23 2013-09-05 Treadstone Technologies, Inc. Corrosion resistant and electrically conductive surface of metal
WO2013124690A1 (en) 2012-02-24 2013-08-29 Teer Coatings Limited Coating with conductive and corrosion resistance characteristics
US8778562B2 (en) 2012-06-11 2014-07-15 GM Global Technology Operations LLC Method of depositing durable thin gold coating on fuel cell bipolar plates
US20160233523A1 (en) * 2013-09-24 2016-08-11 Toyota Jidosha Kabushiki Kaisha Fuel cell separator, fuel cell, and manufacturing method of fuel cell separator

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
Baker, Andrew M., et al. "Nafion membranes reinforced with ceria-coated multiwall carbon nanotubes for improved mechanical and chemical durability in polymer electrolyte membrane fuel cells." The Journal of Physical Chemistry C 118.46 (2014): 26796-26802. *
Lavigne, O., et al. "Cerium insertion in 316L passive film: Effect on conductivity and corrosion resistance performances of metallic bipolar plates for PEM fuel cell application." Surface and Coatings Technology 205.7 (2010): 1870-1877. *
Lee, S. B., et al. "Improved corrosion resistance and interfacial contact resistance of 316L stainless-steel for proton exchange membrane fuel cell bipolar plates by chromizing surface treatment." Journal of Power Sources 187.2 (2009): 318-323. *
U Yin, Bin, et al. "Sliding wear behavior of HVOF-sprayed Cr3C2-NiCr/CeO2 composite coatings at elevated temperature up to 800 C." Tribology letters 37.2 (2010): 463-475 (Year: 2010). *
U Yin, Bin, et al. "Sliding wear behavior of HVOF-sprayed Cr3C2—NiCr/CeO2 composite coatings at elevated temperature up to 800 C." Tribology letters 37.2 (2010): 463-475 (Year: 2010). *
Vernilli, Fernando, et al. "Corrosion behavior in graphite refractories impregnated with ZrO2 and CeO2 carrying solutions." ISIJ international 45.12 (2005): 1871-1877. (Year: 2005). *
Yin, Bin, et al. "Sliding wear behavior of HVOF-sprayed Cr3C2-NiCr/CeO2 composite coatings at elevated temperature up to 800 C." Tribology letters 37.2 (2010): 463-475. (Year: 2010). *
Yin, Bin, et al. "Sliding wear behavior of HVOF-sprayed Cr3C2—NiCr/CeO2 composite coatings at elevated temperature up to 800 C." Tribology letters 37.2 (2010): 463-475. (Year: 2010). *

Also Published As

Publication number Publication date
CN105895927A (zh) 2016-08-24
CN105895927B (zh) 2021-06-11
DE102016102393A1 (de) 2016-08-18
US20160240865A1 (en) 2016-08-18

Similar Documents

Publication Publication Date Title
US10135077B2 (en) Corrosion resistant metal bipolar plate for a PEMFC including a radical scavenger
EP2604717B1 (de) Leitendes element, herstellungsverfahren dafür, separator für brennstoffzellen und festpolymerbrennstoffzelle
JP5226302B2 (ja) 燃料電池用セパレータの製造方法
US10003089B2 (en) Multilayer coating for corrosion resistant metal bipolar plate for a PEMFC
US7674546B2 (en) Metallic separator for fuel cell and method for anti-corrosion treatment of the same
JP5234711B2 (ja) 燃料電池用セパレータおよびその製造方法
WO2005117173A2 (en) A novel approach to make a high performance membrane electrode assembly (mea) for a pem fuel cell
WO2006126613A1 (ja) 燃料電池用セパレータ及びその製造方法
US8785080B2 (en) Passivated metallic bipolar plates and a method for producing the same
JP2016030845A (ja) 導電部材、その製造方法、並びにこれを用いた燃料電池用セパレータおよび固体高分子形燃料電池
US20140295322A1 (en) Material fuel cell separator, fuel cell separator using same, fuel cell stack, and method of producing fuel cell separator material
JP2017073218A (ja) 導電部材、その製造方法、ならびにこれを用いた燃料電池用セパレータおよび固体高分子形燃料電池
JP6759780B2 (ja) 燃料電池用金属セパレータ及びこれを用いた燃料電池
JP5369497B2 (ja) 燃料電池用セパレータ
JP2013143325A (ja) 燃料電池及び燃料電池用セパレータ
WO2009118991A1 (en) Fuel cell separator
JP6947009B2 (ja) 燃料電池用セパレータ及び燃料電池
KR100669319B1 (ko) 연료전지용 금속 세퍼레이터 및 그 제조방법과 이를포함하는 연료전지
WO2013042429A1 (ja) 固体高分子形燃料電池
JP6628122B2 (ja) 導電部材、その製造方法、ならびにこれを用いた燃料電池用セパレータおよび固体高分子形燃料電池
Lim et al. High-performance Ni/Pt composite catalytic anode with ultra-low Pt loading for low-temperature solid oxide fuel cells
JP6512577B2 (ja) 燃料電池構成部品用表面処理部材
JP2020059282A (ja) 導電部材、その製造方法、ならびにこれを用いた燃料電池用セパレータおよび固体高分子形燃料電池
JP2009070680A (ja) 燃料電池用触媒、この触媒からなる燃料電池用膜電極複合体ならびに燃料電池

Legal Events

Date Code Title Description
AS Assignment

Owner name: FORD GLOBAL TECHNOLOGIES, LLC, MICHIGAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HIRANO, SHINICHI;RICKETTS, MARK STEPHEN;GATH, KERRIE K.;AND OTHERS;SIGNING DATES FROM 20150209 TO 20150210;REEL/FRAME:034951/0522

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4